Image-carrying mask photo-sensitive laminate film for use in making an image carry mask

ABSTRACT

A method for engraving and/or etching comprising the steps of: (a) a process for exposing, to light, a layer of a water-soluble resin composition of a laminated photo-sensitive film which comprises a supporting sheet, a image mask-protection layer peelablly adhered to the supporting sheet and a layer of a water-soluble resin composition having photocrosslinkability to thus cause crosslinking of the exposed area of the resin layer to thereby form a predetermined pattern on the resin layer; (b) a process for dissolving out the non-crosslinked portion of the layer of the water-soluble photo-sensitive resin composition by developing the layer with water to thus from an image-carrying mask which is constituted from the crosslinked area of the photo-sensitive resin composition remaining on the image mask-protection layer; (c) a process for adhering the photo-sensitive laminate film on which the images are formed to the surface of a material to be processed; (d) a process for peeling off the supporting sheet from the photo-sensitive laminate film; and (e) a process for engraving and/or etching the material to be processed through the image-carrying mask adhered to the material, makes it possible to engrave and/or etch fine and precises images on the surface of a material to be processed such as glass, metals, plastics or the like.

This is a Division of application Ser. No. 08/116,277 filed Sep. 3, 1993U.S. Pat. No. 5,427,890, which in turn is a continuation of Ser. No.07/668,520, filed Mar. 28, 1991, now abandoned.

TECHNICAL FIELD

The present invention relates to a method for forming images byengraving through sand blasting or by etching with chemicals, forinstance, solutions of etching agents through an image-carrying masksuch as picture images, patterns or letters on the surface of materialsto be processed such as glass, stone, pottery, metals, plastics, woodenmaterials and leather as well as a photo-sensitive laminate film for usein making such an image-carrying mask.

BACKGROUND ART

Conventionally known methods for processing the surface of a materialsuch as glass, a metal or a plastic by engraving images on the surfacecomprise the steps of first forming a resist layer, in the form ofimages, on the surface of a material to be processed and then subjectingthe entire surface inclusive of the surface of the resist layer to sandblasting to thus engrave the surface on which any image is not presentand to thereby form the images thereon. When the material to beprocessed is glass, a treatment of the surface with hydrofluoric acidcan be substituted for the sand blasting treatment and thus desiredimages can be formed on the surface through engraving and/or etching ofthe surface portion on which any image is not present. On the otherhand, when the material to be processed is a copper plate, the surfacecan also be treated with an aqueous solution of ferric chloride and thusthe desired images can be formed through engraving and/or etching of thesurface portion on which any image is not present.

The formation of a resist layer can be performed according to a methodwhich comprises printing desired images on the surface of a material tobe processed with a resist ink according to the screen printing methodto thus form a resist layer in the form of desired images.Alternatively, a resist layer can also be formed by likewise printingimages on the surface of a non-woven fabric of glass fibers according tothe screen printing method and then adhering the resulting non-wovenfabric carrying the printed images to the surface of a material to beprocessed.

Moreover, there have been proposed a variety of methods for preparingimage-carrying masks using liquid photo-sensitive resins. For instance,Japanese Patent Publication for Opposition Purpose (hereunder referredto as "J. P. KOKOKU") No. Sho 46-35681 discloses a method for producingan image carrying mask which comprises the steps of enclosing apredetermined surface area of a material to be processed such as glasswith a rubber frame, directly pouring a photo-sensitive resin into theenclosed area, covering the area with a cellophane film, exposing theresin to light through a negative film carrying pictures and/orpatterns, peeling off the cellophane film and then developing theimagewise exposed photo-sensitive resin to thus form a resist layercarrying the desired images.

Japanese Patent Unexamined publication (hereunder referred to as "J. P.KOKAI") No. Sho 53-99258 discloses a method for producing animage-carrying mask which comprises sandwiching a liquid photo-sensitiveresin composition between two transparent films to form aphoto-sensitive resin composition between two transparent films to forma photo-sensitive layer, exposing the liquid photo-sensitive resin layerto light while coming the composition in close contact with a photomaskcarrying desired pictures and/or patterns, peeling off the transparentfilm on the side of the photomask, removing the unexposed areas of thelayer to thus give the desired image, adhering the resultingphoto-sensitive resin layer on which the images are thus formed to thesurface of a material to be processed so that the face of the former onthe photomask side opposes to the surface of the material and peelingoff the remaining transparent film.

J. P. KOKAI No. Sho 55-96270 discloses a method which comprises thesteps of putting a molding frame which also serves as a spacer on asupport layer (for instance, a polyester film having a thickness of 100μm) capable of being treated by sand-blasting, pouring a liquidphoto-sensitive resin (100% modulus of the resin photo-hardened=500kg/cm²) into the area defined by the molding frame, exposing the resinto light through a film carrying pictures and/or patterns, developingthe exposed resin to thus give a mask carrying the images whichcomprises photo-hardened photo-sensitive resin layer having throughholes corresponding to the images, applying a rubber paste to thereverse face of the support and then adhering the resulting product tothe surface of a material to be processed. In addition, J. P. KOKAI No.Sho 60-104939 discloses a transfer material for forming a mask for sandblasting which comprises a layer carrying a mask-pattern formed from aliquid photo-sensitive resin composition in which the molecularstructure and the properties of its components are specified; asubstrate layer for supporting the layer carrying the mask-pattern; anda support layer which is placed between the layer carrying themask-pattern and the substrate layer, which can be well-adhered to thelayer carrying the mask-pattern but is capable of being peeled off fromthe substrate layer and which can be destroyed through sand blasting. Inthe washing away development of these photo-sensitive resincompositions, it is needed to use an organic solvent such as acetone orbenzene; an alkaline aqueous solution such as an aqueous sodiumhydroxide or sodium borate solution; an alcoholic solution of calciumchloride or an aqueous solution of a surfactant such as a neutraldetergent as a developer.

The present invention has been completed under such circumstances andthe object of the present invention is to provide a method for engravingor etching images with a mask carrying such images as well as aphoto-sensitive laminate film for use in making a mask carrying images,which makes it possible to easily and precisely form fine precise imageson a mask according to the photoprinting technique in the production ofsuch a mask which is used when images are engraved or etched on thesurface of a material to be processed such as glass, a metal or aplastic; which can be handled in the form of a film; which can easily beexposed to light and developed; which can be developed with a developersimply comprising water and whose handling is thus safe and economical;whose surface carrying images obtained after development has strongadhesion and thus can be adhered to the surface of a material to beprocessed without using any adhesive to thus transfer images to thematerial; whose substrate can easily be peeled off after fine picturesand/or patterns are transferred to the material to thus prevent theaberration of the position of an image; and which makes it possible toprevent the removal of fine portions of images during sand blasting tothus allow precise engraving and/or etching.

DISCLOSURE OF THE INVENTION

The method for engraving and/or etching a material according to thepresent invention for achieving the foregoing object comprises thefollowing steps (a) to (e): (a) a process for exposing, to light, alayer of a water-soluble resin composition of a photo-sensitive laminatefilm which comprises a supporting sheet, an image mask-protection layerpeelablly adhered to the supporting sheet and a water-soluble resincomposition layer having photocrosslinkability to thus causecrosslinking of the exposed areas of the resin layer to thereby form apredetermined pattern on the resin layer; (b) a process for dissolvingout the non-crosslinked area on the layer of the water-solublephoto-sensitive resin composition by developing the layer with water tothus form a mask carrying the images which is constituted from thecrosslinked areas of the photo-sensitive resin composition remaining onthe image mask-protection layer; (c) a process for adhering thephoto-sensitive laminate film on which the images are formed to thesurface of a material to be processed; (d) a process for peeling off thesupporting sheet from the photo-sensitive laminate film; and (e) aprocess for engraving and/or etching the material to be processedthrough the image-carrying mask adhered to the material. According tothe foregoing processes, fine and precise images can be easily andprecisely formed on a material to be processed through thephoto-duplicating method. In addition, exposure and developmentprocessings are very simple since the photo-sensitive material is in theform of a film. Moreover, the development processing is safe andeconomical since it is performed with a developer simply comprisingwater. The surface of the image-carrying mask obtained after developmentexhibits strong adhesion and correspondingly the mask can be adhered tothe material to be processed without using any adhesive. Further, thesupporting sheet can easily be peeled off because of a presence of theimage mask-protection layer after fine pictures and/or patterns aretransferred to the material to thus prevent the aberration of theposition of images and the removal of fine portions of the images can beprevented during sand blasting. Thus, the precise engraving and/oretching of a desired patterns and/or pictures can be performed.

In the method of the present invention, the treatment with water in theprocess (b) is preferably performed by previously immersing thephoto-sensitive laminate film which has been exposed to light through apattern to swell the non-crosslinked portion on the layer of thewater-soluble resin composition and then washing with water. Thus, thenon-crosslinked portion on the layer of the water-soluble resincomposition can be completely be removed and hence clear images can beobtained.

In the process (c), the photo-sensitive laminate film is preferablyadhered to a material to be processed while applying a pressure orheating the same. Alternatively, the process (c) can be performed byapplying, to the layer of the crosslinked water-soluble resincomposition, an aqueous solution of sodium periodate, lithium chloride,lithium bromide, lithium nitrate, calcium chloride or ammoniumthiocyanate to swell or solubilize the layer and then adhering thephoto-sensitive laminate film to the material to be processed underpressure.

The process (e) for engraving or etching the material to be processed ispreferably performed according to engraving or etching through sandblast. Likewise, the process (e) may be performed according to theengraving or etching with a chemical.

The photo-sensitive laminate film used in the method for engraving oretching a material to be processed comprises a supporting sheet, animage mask-protection layer peelablly adhered to the supporting sheetand a layer of a water-soluble resin composition havingphotocrosslinkability. The water-soluble resin composition havingphotocrosslinkability of the photo-sensitive laminate film for use inmaking an image carrying mask is a composition comprising a watersoluble polymer and a photocrosslinking agent and preferably comprises acomposition selected from the group consisting of a composition whichcomprises polyvinyl alcohol and a sulfate, hydrochloride, nitrate orphosphate of a condensate of 1-diazophenylamine with paraformaldehyde; acomposition comprising polyvinyl pyrrolidone and sodium4,4-bisazidostilbene-2,2'- disulfonate; and a composition comprisingpolyvinyl methyl ether and mono(di)acryloxyethyl phosphate. Thewater-soluble resin composition having photocrosslinkability may be acomposition comprising a water-soluble polymer having aphotocrosslinkable groups in the molecule selected from polyvinylalcohol which is subjected to modification with acetal to introducestilbazolium groups therein and polyvinyl alcohol to whichN-methylolacrylamide is added. The layer of the water-soluble resincomposition having photocrosslinkability preferably has a thicknessranging from 0.03 to 2 mm. If the thickness of the layer is limited tothe range defined above, the image-mask obtained after development ofthe layer exhibits sufficient resistance to the sand blasting or etchingwith a chemical during the process for engraving or etching the materialto be processed. The image mask-protection layer of the photosensitivelaminate film for making an image-carrying mask is preferably preparedfrom a member selected from the group consisting of polyvinyl alcohol,polyvinyl alcohol derivatives, polyvinyl butyral, ethyl cellulose,cellulose acetate and cellulose nitrate. Moreover, the imagemask-protection layer is made from a material different from that forthe supporting sheet and may be obtained from a member selected from thegroup consisting of polyvinyl chloride, polystyrene and polyamide. Ifthe material for forming the image mask-retention layer is limited tothese specific ones, the image mask-protection layer is weakly adheredto the supporting sheet during the development processing and can easilybe peeled off therefrom, while it is relatively strongly adhered to thelayer of the water-soluble resin composition, i.e., to theimage-carrying mask. The thickness of the image mask-protection layerpreferably ranges from 1 to 30 μm. This is because, if the thicknessthereof falls within the range defined above, the image-carrying maskcan be supported by the layer without causing any breakage and the maskcan easily be removed during the process for engraving and/or etchingthe material to be processed without any difficulty.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a cross-sectional view of the photo-sensitive laminate filmfor image-masks according to the present invention; and FIGS. 2 to 10are diagrams for illustrating, in order, the method for engraving and/oretching with the aid of an image-carrying mask according to the presentinvention.

DESCRIPTION OF PREFERRED EMBODIMENTS

The preferred embodiments of the present invention will hereunder beexplained in more detail, but the present invention is not restricted tothese specific embodiments at all.

FIG. 1 shows the construction of the photo-sensitive laminate film foran image-carrying mask used in the method for engraving and/or etching amaterial with the used of such an image-carrying mask according to thepresent invention. In the photo-sensitive laminate film 10 for animage-carrying mask, an image mask-protection layer 12 is adhered to asupporting sheet 11 obtained from a polyester film having a thickness of75 μm. The image mask-protection layer 12 comprises a layer of ethylcellulose having a thickness of about 5 μm formed according to a coatingtechnique. A layer 13 of a water-soluble resin composition havingphotocrosslinkability having a thickness of 80 μm is formed on the imagemask-protection layer 12, the layer 13 being formed by coating asolution containing polyvinyl alcohol, an ethylene/vinyl acetatecopolymer resin, a diazo resin, a water-dispersible pigment and anon-ionic surfactant, i.e., polyoxyethylene laurylphenyl ether and thendrying the coated layer.

The method for engraving and/or etching a material with animage-carrying mask according to the present invention can be practicedwith the aid of the photo-sensitive laminate film 10 for making animage-carrying mask in accordance with the processes as shown in theattached FIGS. 2 to 10. As is shown in Fig.2, an original positive film15 carrying fine pictures and patterns comes in close contact with thesurface of the water-soluble resin composition-layer 13 of thephoto-sensitive laminate film 10 and is irradiated with light 16 from ametal halide lamp. Then, as shown in FIG. 3, the original positive film15 is peeled off from the photo-sensitive laminate film 10. If theexposed photo-sensitive laminate film 10 is immersed in water 17, theexposed portion thereof 13a is not swollen since it is crosslinked, butnon-crosslinked unexposed portion 13b gets swollen and is soluble inwater as shown in FIG. 4. As shown in FIG. 5, if water 19 is sprayedwith a spraying device 18 to wash away the unexposed portion, only theexposed portion 13a remains as an image-carrying mask and the laminatefilm is thus developed. The resulting product is hot-air dried to givean image-carrying mask 13a on the image mask-protection layer 12 whichis put on the supporting sheet 11.

As is shown in FIG. 6, the image-carrying mask 13a which is stillsupported by the supporting sheet 11 and the image mask-protection layer12 is adhered and contact-bonded to a glass plate 20 while heating withan iron 21. Then, as shown in FIG. 7, the supporting sheet 11 is peeledoff from the image mask-protection layer 12. Further, as shown in FIG.8, the glass plate is engraved or etched by blasting abrasive particles23 through the image mask-protection layer 12 using a sand blastingmachine 22. Thus, the portion of the glass plate 20 to which theimage-carrying mask 13a is adhered is not engraved and/or etched, whileon the portion of the glass plate to which the image-carrying mask 13ais not adhered or which is covered with only the image mask-protectionlayer 12 is engraved and/or etched, the image mask-protection layer 12is completely removed and the surface of the glass plate 20 is engravedand etched as shown in Fig. 9. After the completion of the sand blastingoperation, the remaining abrasive 23 and the image-carrying mask 13a arewashed out so that the glass plate 20 on which the image is engraved oretched is completed as shown in FIG. 10.

The following variations can be made to the foregoing embodiment.

As the supporting sheet 11, there may be used, for instance, apolypropylene film, a polyethylene film, a polystyrene film, a polyvinylchloride film, a polycarbonate film, synthetic paper or paper coatedwith a synthetic resin in addition to the polyester film used in theembodiment. Moreover, the thickness of the supporting sheet 11 may beadjusted within the range of from 50 to 500 μm.

In the foregoing embodiment, the layer 13 of the water-soluble resincomposition used has a thickness of 80 μm. However, the thicknessthereof may be varied between 0.03 to 2 mm and it is thus preferred toproperly control the thickness thereof depending on the depth to beengraved and/or etched so that the image-carrying mask obtained afterdevelopment shows proper resistance to sand blasting or chemicals. Ifthe depth to be engraved is great, the thickness thereof should beadjusted within the range of from 0.1 to 2 mm so as to withstand theprocessing over a long time period, while if the depth to be engraved issmall, it is sufficient to adjust the thickness to 30 to 80 μm.

In the foregoing embodiment, the exposure process shown in FIG. 2 isperformed by irradiating with the light 16 from a metal halide lamp, butit is also possible to use other light sources which emit actinic rayshaving a wave length ranging from 300 to 500 nm such as an arc lamp, axenon lamp or a high pressure mercury lamp.

The development processing as shown in FIG. 5 is carried out by sprayingwater 19 using a spraying machine 18, but it is also effective tolightly rub the surface with a brush or a sponge simultaneously withsuch a spraying operation to wash out the non-exposed portion and tothus develop the laminate film.

In the process shown in FIG. 8, the engraving or etching process isperformed by blasting the abrasive particles 23 with the aid of thesandblasting machine 22, but the etching with a chemical is likewiseeffective. Examples of chemicals used in the engraving or etchingtreatment are an aqueous solution of hydrofluoric acid when thematerials to be processed are glass and stones, an aqueous solution offerric chloride when the materials are copper and copper alloys, andaqueous solutions of hydrochloric acid and sulfuric acid when they areother metals.

The present invention will hereunder be explained in more detail withreference to the following specific examples.

EXAMPLE 1

15 parts by weight of polyvinyl alcohol having an average degree ofpolymerization of 1,700 and a degree of saponification of 88 mole %(available from Shin Etsu Chemical Co., Ltd. under the trade name ofPA-18) was dissolved in 85 parts by weight of water. To the resultingsolution, there were added 120 parts by weight of an ethylene-vinylacetate copolymer emulsion having a solid content of 50% by weight(available from Showa Highpolymer Co., Ltd. under the trade name of EVAAD-50), 5 parts by weight of a diazo resin, 0.2 part by weight of awater-dispersible blue pigment and 1 part by weight of a non-ionicsurfactant, i.e., polyoxyethylene laurylphenyl ether followed by mixingof these to give a mixed solution for forming a layer of aphoto-sensitive resin composition. A polyester film having a thicknessof 75 μm was provided as a supporting sheet. A solution obtained bydissolving ethyl cellulose ("Ethocell STD-10" available from DowChemical Co., Ltd.) in a 1:1 mixed solvent of ethyl alcohol and tolueneso that the concentration of the ethyl cellulose was 10% by weight wasapplied onto the supporting sheet and then dried to give an imagemask-protection layer having a thickness of about 5 μm (determined afterdrying). The mixed solution of the photo-sensitive resin compositionprepared above was applied onto the image mask-retention layer and driedto give a photo-sensitive laminate film comprising a layer of thephoto-sensitive resin composition having a thickness of 80 μm.

An image-carrying mask was prepared from the photo-sensitive laminatefilm thus prepared. An original positive film was closely put on thelayer of the photo-sensitive resin composition of the photo-sensitivelaminate film and the resulting assembly was exposed to light from a 3KW metal halide lamp at a distance of 1 m. Then the exposed film wasdeveloped by immersing in water maintained at ordinary temperature for 3minutes to let the film absorb water and to thus swell the same, thenlightly rubbing with a sponge and washing out to retain only the exposedportion. The developed product was dried with hot air of 50° C. to givean image-carrying mask which carried fine pictures and/or patterns andwhich had still supported by the image mask-protection layer and thesupporting sheet. There was not observed any separation between thesupporting sheet and the image mask-protection layer and between theimage mask-protection layer and the image-carrying mask during thedevelopment processing.

The image-carrying mask was adhered to a glass plate having a thicknessof 8 mm and subjected to contact bonding while applying heat with aniron through the supporting sheet. Then the supporting sheet was peeledoff from the image mask-protection layer. The supporting sheet waseasily separated from the image mask-protection layer, but the adhesionbetween the image mask-protection layer and the image-carrying mask wasstrong and, therefore, there was not observed any aberration of therelative position between the image-carrying mask and the glass plate.

The assembly thus obtained which comprised the glass plate, theimage-carrying mask directly adhered to the glass plate and the imagemask-protection layer was fixed in a sandblasting machine and anabrasive, Alundum #80, was blasted on the glass plate through theimage-carrying mask at a compressed-air pressure of 4 kg/cm² through anozzle having a diameter of 3.6 mm at a distance of about 20 cm to thusperform engraving of the glass plate. The image-carrying mask was notpeeled off and was not damaged at all and the surface of the glass plateto which the image-carrying mask had been adhered was not impaired evenwhen the abrasive was blasted on the assembly for 30 seconds. On theother hand, when the abrasive was blasted on the assembly for 10seconds, the image mask-protection layer was completely removed from theportion of the glass plate which was covered with only the imagemask-protection layer and the glass surface was engraved to a depth ofabout 1 mm. After the completion of the sand blasting operation, theremaining image-carrying mask sufficiently got swollen with water andthen washed away. Thus, the fine picture and patterns of the originalwere faithfully engraved on the glass plate.

EXAMPLE 2.

There was dissolved, in water, a stilbazolium-added polyvinyl alcoholwhich was prepared by subjecting, to a reaction with acetal, polyvinylalcohol having an average degree of polymerization of 1,700 and degreeof saponification of 88 mole % (available from Shin Etsu Chemical Co.,Ltd. under the trade name of PA-18) to add 1.4 mole % ofN-methyl-γ-(p-formylstilyl)-pyridinium methosulfate to thus give asolution having a concentration of 15% by weight. 15 parts by weight ofan acrylate oligomer (available from Toagosei Chemical Industry Ltd.under the trade name of Aronix M-8030), 15 parts by weight ofpentaerythritol triacrylate and 3 parts by weight of2-chlorothioxanthone (available from Nippon Kayaku Co., Ltd. under thetrade name of Kayacure CTX) were added to and dispersed in the foregoingsolution. 55 parts by weight of a 50% by weight polyvinyl acetateemulsion and 0.2 part by weight of a water-dispersible purple pigmentwere added to and mixed with the resulting dispersion to thus prepare amixed solution of a photo-sensitive resin composition. This mixedsolution of the photo-sensitive resin composition was applied onto thesurface of an image mask-protection layer applied to a supporting sheetsimilar to those used in Example 1 and then dried to give aphoto-sensitive laminate film carrying a layer of the photo-sensitiveresin composition having a thickness of 100 μm.

The same procedures used in Example 1 were repeated to give animage-carrying mask using the photo-sensitive laminate film. There wasnot observed any separation between the supporting sheet and the imagemask-protection layer and between the image mask-protection layer andthe layer of the photo-sensitive resin composition, i.e., theimage-carrying mask during the development processing.

The image-carrying mask thus obtained which had been still carried bythe supporting sheet and the image mask-protection layer was adhered toa glass plate having a thickness of 8 mm on which a 1% aqueous solutionof sodium periodate was coated and subjected to contact bonding. Thenthe supporting sheet was peeled off from the image mask-protectionlayer. The supporting sheet was easily be separated from the imagemask-protection layer, but the adhesion between the imagemask-protection layer and the image-carrying mask was strong and,therefore, there was not observed any aberration of the relativeposition between the image-carrying mask and the glass plate.

A 50% by weight aqueous solution of hydrofluoric acid was applied ontothe surface of the resulting assembly which comprised the glass plate,the image-carrying mask adhered to the glass plate and the imagemask-protection layer on the image-carrying mask, on the side of theimage mask-protection layer. After about 2 minutes, the assembly wassufficiently washed with water to wash out the aqueous hydrofluoric acidsolution as well as the remaining image-carrying mask. The portion ofthe glass plate to which the image-carrying mask had been adhered wasnot corroded with the hydrofluoric acid aqueous solution. On the otherhand, the image mask-protection layer was approximately easily beremoved and the portion of the glass plate to which any image-carryingmask had not been adhered, i.e., that covered with only the imagemask-protection layer was corroded and dissolved out to a depth of about50 μm. Thus, the fine picture and patterns of the original werefaithfully etched on the glass plate.

INDUSTRIAL APPLICABILITY

According to the method for engraving and/or etching according to thepresent invention, fine and precise images can be engraved and/or etchedon the surface of a material to be processed such as glass, metals andplastics. The photo-sensitive laminate film for making an image-carryingmask used in the engraving and/or etching method can be handled in theform of a film during preparing the image-carrying mask and thus thehandling thereof during the exposure to light and the development isvery simple. In addition, since the development thereof can be performedwith a developer simply comprising water, the film is safe andeconomical. The image-carrying mask obtained after development can beadhered to a material to be processed without using any adhesive sincethe surface thereof has adherence and does not cause the aberration ofthe position relative to the material to be processed even if it carriesfine pictures and patterns because of a presence of the imagemask-protection layer. Moreover, the image mask-protection layer servesto prevent the separation of fine portions of the image during the sandblasting operation and as a result, precise engraving can be performed.

We claim:
 1. A photo-sensitive laminate film for use in making animage-carrying mask for engraving or etching an image on a substratecomprisinga supporting sheet, a water-insoluble polymeric imagemask-protection layer peelably adhered to said supporting sheet, and asolid layer of a water-soluble resin composition havingphotocrosslinkability applied onto said polymeric image mask-protectionlayer, said water-soluble resin composition comprising polyvinyl alcoholand a sulfate, hydrochloride, nitrate or phosphate of a condensate of1-diazophenylamine with paraformaldehyde, said polymeric imagemask-protection layer being removable from said solid layer by engravingor etching before said solid layer is removed from the substrate onwhich said solid layer is placed during use of the photo-sensitivelaminate film to form an image by engraving or etching.
 2. Thephoto-sensitive laminate film for use in making an image-carrying maskof claim 1 wherein the layer of the water-soluble resin compositionhaving photocrosslinkability has a thickness ranging from 0.04 to 2 mm.3. The photo-sensitive laminate film for use in making an image-carryingmask of claim 1 wherein the polymeric image mask-protection layer isprepared from a member selected from polyvinyl alcohol derivatives,polyvinyl butyral, ethyl cellulose, cellulose acetate and cellulosenitrate and the thickness of the image mask-protection layer ranges from1 to 30 μm.
 4. The photo-sensitive laminate film for use in making animage-carrying mask of claim 1 wherein the polymeric imagemask-protection layer is prepared from a material different from thatfor the supporting sheet and is obtained from a member selected from thegroup consisting of polyvinyl chloride, polystyrene and polyamide andthe thickness of the image mask-protection layer ranges from 1 to 30 μm.